Hydrocarbon conversion process



Oct. 13, 1959 W. M. STRATFORD HYDROCARBON CONVERSION PROCESS 2 Sheets-Sheet 1 Filed Feb. 8. 1956 Oct. 13, 1959 w. M. sTRA'rFoRD HYDROCARBON CONVERSION PROCESS 2 Sheets-Sheet 2 Filed Feb. 8, 1956 United Seates Patent HYDRoeARBoN-coNvERsroN PROCESS:n

William; MfWStratg'ori:NeW-YorkyNX., assigner `to Texaco-Inc., a corplorationgof .Delaware Application Februarys; Alastsseinl ivm-564,227--Vv 4 -c1aim`s.. (ci. ,mf-113) This invention relates y to:` the conversionI vof hydrocarf;

bonsain .thepresence of catalysts in.solid. .pa rticle..form.

Morepa1'.tficular ly,V it lis ,directed `to, a catalytic conversion.

processwhereinthe reaction is catalyzed ,by-a solid; con.

tact :material :in: finely powdered .activate d formgandthe contact rmaterial-is maintained in such form. duringcontinuous use in the process.

Ini 'accor-dance, Withfthel inventiorna slurry..r.ot` flowable mixture; of particulate solid` contact material ,andI Naporzf,

abletliquid, is passed -as-a continuousstream throng-.haa

tubular heatingqzone` under; conditions ...of temperature and pressure such `that ,vaporization .ofthe liquid occurs and,A a continuously `flowing.,gasiform ,stream containingA finely@l powderedsolid contact4 materialsuspended .therein is, established., Feed hydrocarbons, arel` contacted,with

saidl solid material ,inm a r'eactionzone mai,ritained.underI conditions conducive ,for veffecting the .desired :treatment andthe treated hydrocarbons areseparated from the powdered .solid material.V

Advantageously the stream. o vaporized liquid, con.- taining suspended particles ,is subjectedlo .conditions of high velocity. ow and turbulence. such` that Lthesuspended solids, undergo. pulverizatiom for example,f suchf. that,` about 90.-,pe11eentaor ,moreof, the pulverizedmaterial is in the. form of particles of-fleSs .than 50 microns and :pi-effV erablynotexceedingS to micronsize.. `Theatoresaid.

pulverizing,action ,mayroccurI in. ,the..p1 esenceoff the hyv. drocarhons undergoingtreatment. and. advantageously. prior to, passage.through the .reai,on-zone, although itis.

contemplated that such pulverrizingactionrmay take. place Within .the reaction zone.; l

In `one embodimentEoffthe.l invention, particularly. ap.

theresultinastream duringontnueddow athish veloceA ity,V and Athe ,resultingi gniitllre, .passed through',thef.hydro-. Carbon treating ,Zone.maintained,underfthe` desired treatf.

ingstemperature and,.p.r,es,sure..

sirahle` ,to reactivate, the Contact material.. prior" totv such. recycling.- Rectivaticnamar--be Yeietedf.advantanse,0u,slyI by subjecting the contact.,,materiahremoved,fromthe 1reaction zone to partial oxidation with oxygenorfamfoxysat1..-. =,0.111aiming;,sasl Hetulleonsumcdr4 Contact material from the partialcxidationstep iS directed eto;the...1reati. n.

zone to supply a portion of the suspended contact mae 2,908,634 ce Patented .0.ct.. 13,.-` 1959s terial, and a portion of .the .heat .requirements of thehy:A drocarbon.:conversion:step. Gas produced-.in v"the oxidat-ion` step-may.be employed `for` thesynthesis of gasoline and, chemicals. Carbon Emonoxide contained fin; the gas from: theoxidation Vstep mayY be subjected to .re,1 action with steam to produce additional amountsofhyf, drogen-.- Hydrogen; ,Soproduced,istusefulf inthe treatment `of .oils bythydrogenationor .forpthe manufacture of.; chemicals.A

A `feature ofv` the process otfthisrinvention-is thatlcarf; bonaceous catalysts, for exampley coke, may;` be employed,- in hydrocarbon conversion processes. Althoughfcokeror; carbonI Elias f beerrlcnwvnV to` havefcatalytie -activity l fory-the crackingfreation, the,l aromaticnatureoi the higher hoily; ing g products 1. produced;V has mili-tatedj against the-,.:com-v mer eialquseeofzthesefacatalystse Although aromatic hyf; drocarbons;arexlcsirable,in-,gasoline because of their high;-L OCtane numbers; the aromatcs ,are undesirable mfhighea` boilinggfractions, i such,` lasidiesel;y oil, light `fuel oil; Tand Cracking .stockebecause.v ot their; poorburning;andfcraekf: ingcharaeteristics. By, the process f `ofthis,v invention? the advantage .ot producing al high;` octane ,nutnberlmotori fuel g canbe-. exploited @without- A the. 1 production l of large; quantitiesgofzlow quality;h'eavyaoils.'H The high catalytic activity obtained in this process permits the attainment; ofhghconversion. levels not-,otherwiseapossible so. that motorjfuel; in which salomatics are desired lisfthe., primary; Product; anderelativelysmall :quantities .of heavy soil are.- produced. F unther, the-small amount of heavy' oil so.. produeed. may :be -efectivelyi converted, to 4motor t fuell bye recyclngflto the reaction zone.

From the description-herein, itffwilli be. apparent-tm one Vskilled;.,in; `the art` that the; process of this inventioni is 1 adapted-to many hydrocarbon jconversion- -and...treating. processes.:V For example, :but without limitation1thereto thisginventionnmaylfbe advantageously: employed in tsuch'f. diverse., processes= l as catalytic cracking, ,i hydrogenatiom.V dehydrogenation, naphtha reforming, clay treatingaisom-A erizatiom. and desulfurization... Theprocessamay beapf plied.v to the conversion ot vapor-izable liquidhydrocar-V bons including those which', are Aliquidi'ionly under-super= atmospheriefpressure --andf f at slowy temperature,Y for example; propane orgeethane and :those: .which lmay be come pletelyf vaporized` only at high' temperature Iunder` reducedJ pressure,` for-example. gas .oils =and `vacuum distillates. Al-

' though-.conventional catalysts foray given applicationY may;

be employed; the enhanced catalytic: effect resulting from# theehighlyturbulentsowuand catalyst attrition obtainedimthis process` :makes possible the use ofcatalysts f of low' intrinsic activity=whichlarefrelatively inexpensive.- Fon example, in 1 one` embodiment of thisinvention, carbon; innthe. form .of :petroleumY coke, is used Vto- :catalyze thee crackingiof hydrocarbon loil-lvapor.

Anadvantage of .the process of this linvention ris that* the .g catalyst andhydrocarbon- :undergoin g y conversion are brought., into intim-aten contact with f one another. TheN turbulentzowlconditions employed resultin highfrela-- tive :velocities on the :catalyst and vapor and highfrates of massl transfer: Thev hydrocarbon presented 1 to-v -thecatalyst surface is continuous-ly and rapidly changed; Thel l catalyst :attrition continuouslyproduces new catalystusurey face;l The! grinding orbreakngA-up v.of the catalystparr ticlesnot-onlyljresults in the-generationeofnew surface-- but also results the productionof-increasedsurface' fora .givenuweightlof catalyst.`l A' further-eectjof the Y catalyst attrition in-thislprocessis-that accumulation of car-b onaceous .residues on the=catalyst-survface is 'effectivelyvprevented. 1 Similarlyg:.surfaceedeactivation- 1by catalyst4` poisons is tameliorated ,.-bylzthmconstant v,cleansing of `:the- Catalyst surface.

The catalystq activityfot:carbonaceous catalyst mayuben further enhanced by employing Water as slurrying medi- 3 um so that upon vaporization, steam is produced which reacts with the carbonaceous catalyst to further increase its activity. Similarly, partial oxidation of particulate carbonaceous contact material effects activation of the carbonaceous material by reaction of oxygen with the particle surface and the exposure of new active surface.

f The increased catalyst effectiveness, obtained by the process of this invention, may be exploited by using inexpensive catalysts or by using only small quantities of catalysts.

The increased catalyst effectiveness obtained by the process of this invention results in increased exibility of the process in the choice of operating conditions. For example, effective conversion can be obtained at temperatures, pressures, space velocities and catalyst-to-oil ratios not otherwise possible.

Certain of the advantages of the present process are readily seen by comparing the process of this invention with the modern fluid catalytic cracking process. The iluid catalytic cracking process, highly etiicient as it is, nevertheless, requires huge reactors or separators and enormous catalyst inventories. The process of this invention provides a great improvement over the fluid catalytic cracking process in reducing the size of the equipment and the amount of catalyst required, and moreover, furnishes a much more flexible process, particularly with reference to the type of charging stocks which may be used and as to the choice of conditions of operation.

In catalytic cracking, in accordance with this invention, catalyst vis slurried with oil. The catalyst may be in relatively coarse particle form but capable of being slurried in the oil and carried in suspension therein. The slurry or suspension is pumped to the tubular heater at a sufiicient velocity to maintain the catalyst in suspension in the liquid oil, for example 0.5 to 20 feet per second, preferably 2 to 10 feet per second, and is directed through the heater with vaporization and resultant acceleration in velocity. The rate of flow through the elongated heater is such that conditions of turbulent flow are maintained as vaporization proceeds and the catalyst is pulverized or comminuted by the attrition of the catalyst particles. Sufficient heat is applied in the heater to effeet vaporization and to heat the catalyst to the desired catalytic conversion temperature.

i- The conversion temperatures suitable for catalytic cracking operation are generally in excess of 800 F. and are usually in the range of 900 F. to. 1000 F. or even higher. With high rates of initial flow to the heater and with the increase in volume resulting from vaporization, extremely high velocities are obtainable in the vaporizing section of the heater. The velocity of ilow in the vapor section of the heater should be at a minimum of about V25 feet per second, which is about the minimum velocity for carrying many materials through a tube in suspension in vapor. As a practical matter, to assure rapid and substantial attrition for commercial operation, the velocity is usually maintained above 150 feet per second and may run considerably higher up to some 1800 feet per second. In fact, velocities of such magnitude as to be within sonic rates of ow may be used with advantage. High inlet pressures to the heater are employed, such as pressures of 500 to 1000 pounds per square inch with outlet pressures of atmospheric pressure to about 100 p.s.i.g. The differential pressure through the heater results in high velocity and turbulent conditions of flow and the relatively low pressure at the outlet promotes vaporization and further increase in velocity.

By way of example, a suspension in gas oil of powdered coke of average particle size of 100 microns is introduced to a tubular heater of uniform tube diameter at the rate of 20 feet per second. Heating the stream to temperatures suitable for cracking of about 900 to 1000 F. and at a discharge pressure of about 30 p.s.i.g. raises the linear velocity to the order of 1500 feet per sec- I ond in the vaporizing section. At this velocity, great turbulence exists and attrition of the catalyst effectively comminutes the catalyst to an average particle size of a few microns, rthus greatly increasing the catalytic surface area and reducing the contact time required to obtain a given amount of catalytic cracking.

Pressures over a wide range may be advantageously employed for catalytic cracking by the process of this invention. For example, pressures of one or two atmospheres, as used in conventional uidized catalytic cracking, or higher pressures on the order of 10 to '50 atmospheres may be employed. Yields of equal quallty motor gasoline at constant gas oil conversion are increased by virtue of conducting the process of this invention at a pressure of 10 atmospheres as compared with conventional cracking pressures.

In one method of operation, in accordance with the invention, carbonaceous catalyst, such as petroleum coke, is slurried with water and passed through a tubular heater at a high rate of flow with resultant comminution of the coke particles and the concomitant activation of the coke by the steam. The oil charging stock is separately vaporized and the stream of oil vapors is merged with the fluidized and activated coke stream to effect cracking of the oil vapors.

In dehydrogenating normally gaseous hydrocarbons, such as butane or a mixture of butane and propane, an advantageous operation is to slurry the catalyst with liquid butane. The slurry is passed through a tubular heater at a velocity above about feet per second with complete vaporization of the hydrocarbon. Turbulent ow conditions are produced with resultant comminution of the catalyst and dispersion thereof in the gaseous stream. The catalyst-containing stream of vaporized hydrocarbons and the comminuted constituents are subjected to a temperature in the range of about 600 to 1400 F. at subatmospheric pressure or pressures up to about 50 p.s.i.g. to effect the desired dehydrogenation.

From the foregoing description, it will be evident that in the practice of the invention it is necessary to have high rates of flow and highly turbulent conditions in order to effect the desired comminution of the catalyst. To effectively obtain these conditions, the materials are passed through tubular heaters of restricted diameters, such yas internal diameters of some 1/2 to 3 inches. In order to avoid erosion of the tubes, insofar as is possible it is desirable to construct the tubular heater with a minimum of sharp bends and to streamline the conduit as far as is practicable. There is, no doubt, some comminution of the catalyst produced by contact with the metal walls of the conduit, but it is desirable to minimize this contraction insofar as it is possible and to rely on the attrition of the particles to effect the desired comminution. However, it has also been found that erosion may be minimized by owing the dispersion at relatively low velocity through a tubular heating zone and then increasing the turbulence and absolute velocity of the particles, or their relative velocities with respect to one another, in a localized zone. One way proposed for locally increasing absolute velocity is to pass the dispersion of solid in vapor through a convergent-divergent nozzle at supersonic velocity while the velocity upstream of the nozzle is maintained relatively low, such as 100 feet per second or less, to prevent erosion. Another procedure for locally increasing relative velocities is to divide the slurry stream or the flowing dispersion stream into two parts, and then to impinge the resulting two flowing streams of solid dispersed in vapor against one another at high velocity by passing them through a pair of nozzles which are opposed to one another at 180, more or less, as described in U.S. application Serial No. 360,188,

filed June 8, 1953, now abandoned.

In the drawings: Y

Figure 1 is a flow diagram of a preferred embodiment of the invention as applied to catalytic cracking.

l Figurers ardow-ediagram of-a modificationfofthe` invention in which thecatalyst is separately slurried and from thettank lfandrapidly circulating it `vback-to the` from the circulating lineand' directs -it through a coil 17 disposed ina 'furnace-1&1 Coil- 17fcomprisesboth a heating-zone and a-` Vtubular reaction` zone. In transit throughh lthefcoil; the oil -is vaporizedjand the velocity" inereasedtof-a` rateaboveabout4 150`-feetper second.

Conditions ofturbulent llow prevail,- theV catalystris 1cornmiuted, and'lthe oil-e is subjected to effective'` catalytic cracking-.W 'Ilhe'stream of reaction products passes throughl a-transfer----line 19-to Aa'cyclonegseparator 20.- Inthe separator 20 separation `ofcatalyst fromA oil vapors'and gases takes *placer The catalyst, withr which may be included-heavyvresidual products iof reaction, is withdrawn through a line 22. The separated vapors andl gases pass toafractionator 23 wherein'the vapors are fractionated tof-obtain-desiredefractionssuch as a heavy or fuel oil' frotionvwithdrawn1 asbottoms through line 24;'V an in termediate-on-gas--oil fractionetakenoi `through line 25, and-anj overheadfraction,` gasoline or a naphtha, Vwhich is=condensedf=ini-the -condenser -26 and collected `in a re-A ceiving drum orA gas separator 27.

Ilfthe systemof'fFigure 2, a `slurry tank`130tis provided withfstirringoragitating -means-31: Solid catalyst, for

example coke-or-"a conventional cracking catalyst, is

adniittedwthrough a `hopper--32"and a liquidmedium, such as oil or water is introduced througha line 33;" By-means of a circulatnglineaflsandyzpump 35,1;a1slurryor suspension of thecatalyst is maintained inrapid circulation. Slurry from the circulating line 34 ilows through line 36 to=-heatingrcoil-37disposedinea furnace 38. InIIanSit throughtther-coil,V the-liquid-medium Vis Vsubstantially all vaporized .tof'ffonn--a dispersion-of catalyst particles in resulting -va-por.- Thee-dispersion is separated into two streamstin lines 439and40and the resulting streams im.- pinged onetagainsbthe-other by--passing them through a pain; of. .opposed A nozzles-e 41 and- 42. The comminuted eilent `in the form -of--a fluidized vstream of catalyst vin the'lfvaporsuisdischarged-througha transfer line 43. to separator.44:2l Separator 44-is -acyclone separator which may1sbe=used-to remove-excess steam when water` is `used asrslurryingvmedium-Yor-it-may 4be used `to eifect separa.- tion; of San tunusuallyV `tine fraction of the comminuted solids astwill. fbe. described-- hereinafter. lThe amount ,of water required. .foi-satisfactoryslurry` feeding may. pro-` ducezmoretrsteam..thanis required Afor satisfactory suspension of the catalyst in vapor or more steam than is desired in the subsequent reaction zone. When separator 44 is used to remove excess steam, the steam is vented through line 45, and is discharged through line 45a for process or heating purposes not shown. A concentrated suspension of catalyst is withdrawn from separator 44 and is passed'through line 46 to transfer line 52. Under conditions of operation such that expansion of the dispersed catalyst particles through the grinding nozzles reduces the temperature of the suspended catalyst to a temperature below the desired conversion temperature, the separated catalyst stream may be reheated by passing through line 46a to heating coil 47. Effluent from heating coil 47 is discharged through transfer line 48 to line 52.

The hydrocarbon oil to be subjected to catalytic cracking, from an external source not shown, is charged by pump'V 49 through a heating coil-f507 disposed-"insa 'furnace- 51. Inytransit through the coilthe oilis preheated and# Inf the :case-ofA thelighter charging stocks, the oil is completely vaporized-inthei f coil 50 `and in the case of heavy residualstocks, the oil is ,partially vaporized. Thel coileflluent passes through a transfer line v52wherein it is co-mingled with the cata-v lyst stream from lineV 48 `or 46a andthe co-mingled con;

subjectedV to vaporization.

stituents flow to reactor 53. Reactor53 may be disposed as an upow reactor asl shown Vin FigureZ so that-theconcentration of catalyst and yresidence time of the cata-- lyst inthe `reaction zone is greater than that'of the oil j vapors undergoing conversion.

So long as the velocity of the vapors inthe-reactor exceeds the terminal velocity of the catalystparticles-inthe vapor under the force of gravity, the catalystwillf remain dispersed in the vaporous stream; ,s However, ifv the reactor diameter is selected so that-'the vapor veloc ity is less thanthe vaforesaid terminal velocity,` a dense phase ,of fluidized particles is formed. In the latter case, catalyst can be withdrawn from the dense phaseof the reactor substantiallyfree from the reactor vapors and the reactor vapors may be separatelywithdrawn substantiallyV free of catalyst in a manner similar to'that employed Ain the well known downow fluid catalytic cracking process.V

If desired, however, the reactor may be disposed so; that thedispersion of catalyst in rvapor is introduced gat the top of the reactor and removed from the bottom.

In which case, the catalyst velocity through the reaction.,y zone is at least as great as that ofthe oil vapors. TheV gasiform reaction products and Vcatalyst suspended `therein are withdrawn from the reactor-throughV line 54andl are passed to desuperheater 55. Desuperheater 55servesl to cool the reaction products to liquefy` at `least the highest f boiling Areaction products and to separate the catalyst' from the remainingproducts as a slurryin the liqueiied high boiling fraction. This is accomplished -bycirculatj ing slurry by pump 56 through lines 57^ and 58and cooler 59 toa distributor tray in desuperheater 5S. The cooled slurry cascades through suitable packing orbafes countercurrent .to the incoming hot reaction products and catalyst. Reaction products free-offentrainedrcatalyst are withdrawn through line 60 to external vfractionation not shown where gas, gasoline, middle distillates and;oth er desired fractions are separated. Catalyst-heavy oill slurry may be ,withdrawn ,through line 61' for fuel vor other use not shown. In the alternative, at Lleast a portion of vthe` catalyst-heavy oil slurry may berecycle'd through linesA 62 yand 63to slurry line 36 in order to achieve furtherV conversion of the heavy oil and reuse of the catalyst;

vert all of the heavy oil and a part of the carbonaceous catalyst to a mixture of hydrogen and carbon monoxide, usually refer-red to as synthesis gas. Eluent from gasier 65 is discharged through line 67 to cyclone separator 68. Synthesis gas separated in separator 68 is discharged through line 69 to other uses not shown. Hot unconverted catalyst is withdrawn from separator 68 through line 70 and is combined with the feed to 4reactor 53 in line 52 to provide a highly active catalyst and a part of the heat required for the cracking reaction.

As described above, separator 44 may be employed to separate a fine fraction of comminuted solids. In this case tine solids are removed from separator 44 entrained in the overhead gas in line 45, and the comminuted solids of larger particle size are withdrawn from the bottom of separator 44 through line 46 for use in the process as previously described. Entrained solids are passed through line 45 and 4511 to separator 71. Separator 71 may comprise, for example, an electrostatic precipitator, bag filter, or other apparatus adapted for the separation of fine solid particles from gas or vapor. Fine product is Withdrawn from separator 71 through line 72 and gas or vapor is discharged through line 73. The process of this invention may be employed generally to produce tine powders of solid catalysts useful for hydrocarbon conversion. This method of producing fine powders is particularly useful when carbonaceous catalysts are employed to produce a novel finely divided carbonaceous composition. This novel, finely divided carbonaceous material can be used effectively in many applications heretofore requiring carbonaceous blacks, for example carbon black and lamp black. Depending upon the conditions of the grinding operation and the fractional separation employed, fine particles in the range of about to 30 millimicrons may be produced. Since the fine product is fractionally separated from the ground total product, the fine product comprises yparticles of substantially uniform size.

Although the invention has been described in connection with carbon or carbonaceous catalysts, it will be understood that more conventional catalysts such as silica alumina, molybdena alumina or chromia alumina may be used in the process of this invention. Also, when coke or carbonaceous catalysts are used, other catalytically active materials may be added as promoters or conjunctive catalysts.

Mention has already been made of forming a slurry of the solid particles in vaporizable liquid and then heating the resulting slurry mixture. As an alternative, a flowable paste of the particles in the liquid may be formed and this paste then injected into or mixed with a owing stream of hot vapor under conditions to form a stream of particles dispersed in gasiform fluid. The stream containing dispersed particles is then brought into Contact with the feed hydrocarbon before or after passage through a uid energy grinding zone. As previously disclosed, the hot vapor may be all or a portion of the feed hydrocarbon stream.

Obviously many modifications and variations of the invention as hereinbefore set forth may be made without departing from the spirit and scope thereof and only such limitations should be imposed as are indicated in the appended claims.

I claim:

1. A process for the conversion of hydrocarbons which comprises forming a slurry of coke particles in a vaporizable liquid hydrocarbon, forcing said slurry into and through a heating zone, heating said slurry during passage through said heating zone to a temperature within the range of about 900 to 1000 F., vaporizing substantially all of said hydrocarbon component during passage through said heating zone forming therein a dispersion of coke particles in resulting vapor, passing said dispersion through a high velocity grinding zone at a velocity in excess of 150 feet per second, effecting cracking of said hydrocarbon and grinding of said coke,

and discharging products of cracking and ground coke Y gas oil, forcing said slurry into and through a heating zone, heating said slurry during passage through said heating zone to a temperature Within the range of about 900 to 1000" F. forming therein a dispersion of coke particles in resulting vapor, and passing said dispersion through a high velocity grinding zone at a velocity in excess of 150 feet per second, thereby effecting comminution of said coke and cracking of said gas oil.

3. In a process for cracking a liquid hydrocarbon in the presence of a solid carbonaceous catalyst, the improvement which comprises forming a liowable mixture of coke of about microns average particle size in a vaporizable liquid hydrocarbon, introducing said mixture into an elongated heating zone at a velocity within the range of about 0.5 to 20 feet per second, vaporizing said liquid hydrocarbon forming a dispersion of said coke in hydrocarbon vapor, passing said dispersion through a portion of said heating zone at a temperature Within the range of 900 to 1000o F. and at a velocity in excess of about feet per second effecting concomitant comminution of said coke and cracking of said hydrocarbon.

4. In a process for cracking a gas oil in the presence of catalytically active coke, the improvement which comprises forming a owable mixture of coke of about 100 microns average particle size in said gas oil, introducing said gas oil into an elongated heating zone at a velocity of about 20 feet per second, vaporizing said gas oil forming a dispersion of said coke in gas oil vapor, passing said dispersion through a portion of said heating zone at a temperature Within the range of about 900 to 1000 F. and at a velocity of about 1500 feet per second effecting concomitant comminution of said coke and cracking of said gas oil.

References Cited in the file of this patent UNITED STATES PATENTS 2,364,145 Huppke et al Dec. 5, 1944 2,377,716 Read June 5, 1945 2,384,967 Schumacher et al Sept. 18, 1945 2,428,715 Marisic Oct. 7, 1947 2,433,798 Voorhees Dec. 30, 1947 2,471,104 Gohr May 27, 1949 2,592,591 Odell Apr. 15, 1952 2,598,309 Say et al. May 27, 1952 2,605,214 Galstaun July 29, 1952 2,619,449 Sweetser Nov. 25, 1952 2,721,168 Kimberlin Oct. 18, 1955 2,738,307 Beckberger Mar. 13, 1956 2,739,104 Galbreath et al. Mar. 20, 1956 2,743,171 Janeway Apr. 24, 1956 2,753,296 Sellers July 3, 1956 2,789,942 Cooper et al. Apr. 23, 1957 

1. A PROCESS FOR THE CONVERSION OF HYDROCARBONS WHICH COMPRISES FORMING A SLURRY OF COKE PARTICLES IN A VAPORIZABLE LIQUID HYDROCARBON, FORCING SAID SLURRY INTO AND THROUGH A HEATING ZONE, HEATING AN SLURRY DURING PASSAGE THROUGH SAID HEATING ZONE TO A TEMPERATURE WITHIN THE RANGE OF ABOUT 900 TO 1000*F., VAPORIZING SUBSTANTIALLY ALL OF SAID HYDROCARBON COMPONENT DURING PASSAGE THROUGH SAID HEATING ZONE FORMING THEREIN A DISPERSION OF COKE PARTICLES IN RESULTING VAPOR, PASSING SAID DISPERSION THROUGH A HIGH VELOCITY GRINDING ZONE 